Zeolite composite, method for making and catalytic application thereof

ABSTRACT

A catalytic material includes microporous zeolites supported on a mesoporous inorganic oxide support. The microporous zeolite can include zeolite Beta, zeolite Y (including “ultra stable Y”—USY), mordenite, Zeolite L, ZSM-5, ZSM-11, ZSM-12, ZSM-20, Theta-1, ZSM-23, ZSM-34, ZSM-35, ZSM-48, SSZ-32, PSH-3, MCM-22, MCM-49, MCM-56, ITQ-1, ITQ-2, ITQ-4, ITQ-21, SAPO-5, SAPO-11, SAPO-37, Breck-6, ALPO 4 -5, etc. The mesoporous inorganic oxide can be e.g., silica or silicate. The catalytic material can be further modified by introducing some metals e.g. aluminum, titanium, molybdenum, nickel, cobalt, iron, tungsten, palladium and platinum. It can be used as catalysts for acylation, alkylation, dimerization, oligomerization, polymerization, hydrogenation, dehydrogenation, aromatization, isomerization, hydrotreating, catalytic cracking and hydrocracking reactions.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a continuation of U.S. patent applicationSer. No. 10/691,358 filed Oct. 22, 2003 and now issued as U.S. Pat. No.7,084,087, which is a continuation-in-part of U.S. patent applicationNo. 09/995,227, filed on Nov. 27, 2001 and now issued as U.S. Pat. No.6,762,143, which is a continuation in part of U.S. patent applicationNo. 09/390,276 filed Sep. 7, 1999, and now issued as U.S. Pat. No.6,358,486, to which priority is claimed, both of said applications beingherein incorporated by reference.

BACKGROUND

1. Field of the Invention

The present disclosure is related to a unique, catalytic materialcontaining zeolite embedded in a catalyst support, and particularly to amicroporous zeolite embedded in a mesoporous support.

2. Background of the Art

Many of today's hydrocarbon processing technologies are based on zeolitecatalysts. Zeolite catalysts are well known in the art and possesswell-arranged pore systems with uniform pore sizes. However, thesematerials tend to possess either only micropores or only mesopores, inmost cases only micropores. Micropores are defined as pores having adiameter of less than about 2 nm. Mesopores are defined as pores havinga diameter ranging from about 2 nm to about 50 nm. The small microporeslimit external molecules to access the catalytic active sites inside ofthe micropores or slow down the diffusion process to the catalyticactive sites. Many catalytic reactions of hydrocarbons are mass-transferlimited, so the effective utilization of the catalyst is reduced. Onesolution is to reduce the catalyst particle size, thereby shortening thediffusion path and increasing the external surface of the catalystparticles.

In practice, the small zeolite catalyst particles cannot be directlyused because the dust-like material is difficult to handle, and it wouldcreate a pressure drop problem in a fixed bed reactor. As such, thezeolites are usually mixed with an inorganic oxide and extruded into acertain shape and size. The calcined, finished catalyst then has goodphysical integrity and a porous structure. However, depending upon thespecific reaction, the binder can impose a mass-transfer limitation tothe zeolite particles buried inside the binder. If the less porousbinder can be replaced by a highly porous support, the accessibility ofexternal molecules to active sites in zeolites will be increased.

It is highly desired to have a catalyst with ideal pore sizedistribution, which will facilitate transport of the reactants to activecatalyst sites and transport of the products out of the catalyst.

SUMMARY OF THE INVENTION

A material useful in catalytic processing of hydrocarbons is providedherein. The material comprises a zeolite, and a porous inorganic oxidethat includes at least 97 volume percent mesopores based on themicropores and mesopores of the inorganic oxide. The zeolite ispreferably a microporous zeolite such as for example, zeolite Beta,zeolite Y (including “ultra stable Y”—USY), mordenite, Zeolite L, ZSM-5,ZSM-11, ZSM-12, ZSM-20, Theta-1, ZSM-23, ZSM-34, ZSM-35, ZSM-48, SSZ-32,PSH-3, MCM-22, MCM-49, MCM-56, ITQ-1, ITQ-2, ITQ-4, ITQ-21, SAPO-5,SAPO-11, SAPO-37, Breck-6, ALPO₄-5, etc. A method for making and methodfor using the material are described herein. The zeolite particles aresurrounded by randomly interconnected mesoporous channels, which providehigh accessibility to the zeolite. In some cases the interaction betweenthe zeolite particle and mesoporous support may modify the properties ofboth zeolite and mesoporous support to certain extent.

The catalytic material described herein advantageously facilitates thetransport of reactants to active catalyst sites and is about 2-5 timesmore active than the zeolite used alone, depending on the specificapplications.

BRIEF DESCRIPTION OF THE DRAWINGS

Several embodiments are described below with reference to the drawingswherein,

FIG. 1 shows the following: an X-ray diffraction (XRD) pattern of Sample1 containing a mesoporous inorganic oxide support with zeolite beta(plot 1-a), an XRD pattern of zeolite beta (plot 1-b), and an extendedscanning time (EST) XRD image of Sample 1 (plot 1-c);

FIG. 2 is a high resolution transmission electron microscopy (TEM) imageof the mesoporous inorganic oxide support with zeolite beta (Sample 1),and an inset showing an electron diffraction pattern of the zeolitedomains;

FIG. 3 is a chart showing the temperature programmed desorption of NH₃(NH₃-TPD) analysis of the mesoporous inorganic oxide support withzeolite beta (Sample 1), and a comparison sample containing no zeolitebeta;

FIG. 4 is a graph showing the mesopore size distribution of the materialproduced in Examples 3, 4, and 5 herein, and of pure zeolite beta;

FIG. 5 is a chart showing the XRD patterns of the materials produced inExamples 2 to 5 herein, as well as pure zeolite beta;

FIG. 6 shows the XRD patterns of the mesoporous material (plot 6-a),MCM-22 (plot 6-b), and the composite material of Example 7 (plot 6-c);

FIG. 7 shows the mesopore size distribution of the materials produced inExamples 7, 8 and 10;

FIG. 8 shows the XRD patterns of the mesoporous material (plot 8-a),pure MCM-56 (plot 8-b), and Composite 8 (plot 8-c);

FIG. 9 shows the XRD patterns of pure ITQ-2 zeolite (plot 9-a), themesoporous material (plot 9-b), the Composite 9 material (plot 9-c), andthe Composite 10 material (plot 9-d);

FIG. 10 shows the pseudo-first order reaction rate constant based on themass of zeolite for n-hexane cracking at 538° C. with Samples 3, 4, 5and pure beta zeolite;

FIG. 11 shows the NH₃-IR spectra of the materials produced in Examples 4and 5; and,

FIG. 12 shows the XRD patterns of the materials produced in Examples 18herein (plot 12-a), as well as pure USY zeolite (plot 12-b).

DETAILED DESCRIPTION OF PREFERRED EMBODIMENT(S)

The catalyst described herein includes a microporous zeolite embedded ina mesoporous support. The microporous zeolite can be any type ofmicroporous zeolite. Some examples are zeolite Beta, zeolite Y(including “ultra stable Y”—USY), mordenite, Zeolite L, ZSM-5, ZSM-11,ZSM-12, ZSM-20, Theta-1, ZSM-23, ZSM-34, ZSM-35, ZSM-48, SSZ-32, PSH-3,MCM-22, MCM-49, MCM-56, ITQ-1, ITQ-2, ITQ-4, ITQ-21, SAPO-5, SAPO-11,SAPO-37, Breck-6 (also known as EMT), ALPO₄-5, etc. Such zeolites areknown in the art, and many are commercially available. In thisinvention, the zeolite can be incorporated into the mesoporous supportor can be synthesized in-situ in the catalyst support.

A metal can be incorporated into the zeolite framework as substitutionsof lattice atoms and or located inside the micropores of the zeolite.Such metals can include, for example, aluminum, titanium, vanadium,zirconium, gallium, boron, manganese, zinc, copper, gold, lanthanum,chromium, molybdenum, nickel, cobalt, iron, tungsten, palladium andplatinum. These metals can be incorporated as combinations, e.g., NiMo,NiW, PtPd, etc.

The catalyst support is preferably a three-dimensional mesoporousinorganic oxide material containing at least 97 volume percent mesopores(i.e., no more than 3 volume percent micropores) based on micropores andmesopores of the organic oxide material (i.e., without any zeoliteincorporated therein), and generally at least 98 volume percentmesopores. A method for making a preferred porous silica-containingcatalyst support is described in U.S. Pat. No. 6,358,486. The averagemesopore size of the preferred catalyst, as determined fromN₂-porosimetry, ranges from about 2 nm to about 25 nm.

Generally, the mesoporous inorganic oxide is prepared by heating amixture of (1) a precursor of the inorganic oxide in water, and (2) anorganic templating agent that mixes well with the oxide precursor or theoxide species generated from the precursor, and preferably formshydrogen bonds with it. The starting material is generally an amorphousmaterial and may be comprised of one or more inorganic oxides such assilicon oxide or aluminum oxide, with or without additional metaloxides. The silicon atoms may be replaced in part by other metal atoms.These metals include, but are not limited to, aluminum, titanium,vanadium, zirconium, gallium, boron, manganese, zinc, copper, gold,lanthanum, chromium, molybdenum, nickel, cobalt, iron, tungsten,palladium and platinum. They can be incorporated into the organic oxideinside at least one mesopore wall and/or at least one mesopore surface.The additional metals may optionally be incorporated into the materialprior to initiating the process for producing a structure that containsmesopores. Also after preparation of the material, cations in the systemmay optionally be replaced with other ions such as those of an alkalimetal (e.g., sodium, potassium, lithium, etc.).

The organic templating agent, a mesopore-forming organic compound, ispreferably a glycol (a compound that includes two or more hydroxylgroups), such as glycerol, diethylene glycol, triethylene glycol,tetraethylene glycol, propylene glycol, and the like, or member(s) ofthe group consisting of triethanolamine, triisopropanolamine, sulfolane,tetraethylene pentamine and diethylglycol dibenzoate. Preferably, theorganic templating agent has a boiling point of at least about 150° C.

The mesoporous catalyst support is a pseudo-crystalline material (i.e.,no crystallinity is observed by presently available x-ray diffractiontechniques). The diameter of the mesopores is preferably from about 3 nmto about 25 nm. The surface area of the catalyst support, as determinedby BET (N₂), preferably ranges from about 400 m²/g to about 1200 m²g.The catalyst pore volume preferably ranges from about 0.3 cm³/g to about2.2 cm³/g. According to one embodiment the materials have one peak inthe XRD diffraction pattern where 2θ is between 0.5 and 2.5 degrees.

The catalyst's zeolite content can range from less than about 1% byweight to more than about 99% by weight. However, it is preferably fromabout 3% by weight to 90% by weight, and more preferably from about 4%by weight to about 80% by weight. The catalyst with zeolite includedpreferably contains no more than about 10 volume percent of micropores.

More particularly, the method for making the catalyst includessuspending a zeolite in water. An inorganic oxide precursor is thenadded to the water and mixed. The inorganic oxide precursor can be asilicon containing compounds such as tetraethyl orthosilicate (TEOS) ora source of aluminum such as aluminum isopropoxide, which reacts withwater to form the inorganic oxide. TEOS and aluminum isopropoxide arecommercially available from known suppliers.

The pH of the above mixture is preferably kept about 7.0. Optionally,the aqueous mixture can contain other metal ions such as those indicatedabove. After stirring, an organic templating agent is added and mixedinto the mixture. The organic templating agent helps to form themesopores during a pore-forming step, as discussed below. The organictemplating agent should not be so hydrophobic so as to form a separatephase in the mixture. The organic templating agent can be one or morecompounds as listed above. The organic templating agent is preferablyadded by dropwise addition with stirring to the aqueous inorganic oxidesolution. After a period of time (e.g., from about 1 to 4 hours) themixture forms a thick gel. The mixture is preferably stirred during thisperiod of time to facilitate the mixing of the components. The solutionpreferably includes an alcohol, which can be added to the mixture and/orformed in-situ by the decomposition of the inorganic oxide precursor.For example, TEOS, upon heating, produces ethanol. Propanol may beproduced by the decomposition of aluminum isopropoxide.

Optionally, the zeolite can be altered by pretreatment. For example, inone type of pretreatment the zeolite can be modified by ion exchange,impregnation, immobilization of functional species and steaming. Also,lamellar structured zeolites such as MCM-22 can be exfoliated byappropriate treatments to new types of zeolites such as ITQ-2. Certaintreatments, such as intercalation or delamination, can be carried out byswelling the precursors with cationic surfactants in the presence ofalkali (Corma et al. J. Catal. 191 (1): 218-224, 2000). Optionally, theswollen materials can be delaminated by, for example, ultrasonictreatment with or without mechanical agitation. Finally, the delaminatedmaterials can be separated and calcined to form a new type of zeolite.

This invention provides a new approach to incorporate or stabilize orsupport the delaminated zeolite into a porous matrix/support. Theswollen materials can be suspended in water first and then an inorganicoxide precursor, or the mesoporous support can be added to the water andmixed as described above. Optionally, the delamination of the swollenmaterials can be carried out by ultrasonic treatment with or withoutmechanical agitation during the addition of other components (e.g.,pore-forming agent) and/or during the gel formation process. After gelformation, a new type of zeolite, differing from the zeolite addedbefore swelling, can be incorporated into the gel.

The gel is then optionally aged at a temperature of from about 5° C. toabout 45° C., preferably at room temperature, to complete the hydrolysisand polycondensation of the inorganic oxide source. Aging preferably cantake place for up to about 48 hours, generally from about 0 hours to 30hours, more preferably from about 2 hours to 20 hours. After the agingstep the gel is heated in air at about 98° C. to 100° C. for a period oftime sufficient to dry the gel by driving off water (e.g., from about 6to about 48 hours). Preferably, the organic templating agent, whichhelps form the mesopores, should remain in the gel during the dryingstage. Accordingly, the preferred organic templating agent has a boilingpoint of at least about 150° C.

The dried material, which still contains the organic templating agent,is heated to a temperature at which there is a substantial formation ofmesopores. The pore-forming step is conducted at a temperature above theboiling point of water and up to about the boiling point of the organictemplating agent. Generally, the mesopore formation is carried out at atemperature of from about 100° C. to about 250° C., preferably fromabout 150° C. to about 200° C. The pore-forming step can optionally beperformed hydrothermally in a sealed vessel at autogenous pressure. Thesize of the mesopores and volume of the mesopores in the final productare influenced by the length and temperature of the hydrothermal step.Generally, increasing the temperature and duration of the treatmentincreases the mesopore diameter and the percentage of mesopore volume inthe final product.

After the pore-forming step, the material is calcined between about 300°C. to about 1000° C. The calcination temperature is preferably fromabout 400° C. to about 700° C., and more preferably from about 500° C.to about 600° C. The calcining temperature is maintained for a period oftime sufficient to effect removal of the organic templates/pore formingagents. The duration of the calcining step typically ranges from about 2hours to about 40 hours, preferably 5 hours to 15 hours, depending, inpart, upon the calcining temperature.

To prevent hot spots the temperature should be raised gradually.Preferably, the temperature of the catalyst material should be ramped upto the calcining temperature at a rate of from about 0.1° C./min. toabout 25° C./min., more preferably from about 0.5° C./min. to about 15°C./min., and most preferably from about 1° C./min. to about 5° C./min.

During calcinion the structure of the catalyst material is finallyformed while the organic molecules are expelled from the material anddecomposed.

The calcinating process to remove organic templating agent can bereplaced by extraction using organic solvents, e.g., ethanol. In thiscase the templating agent can be recovered for re-use.

Also, the catalyst powder of the present invention can be admixed withbinders such as silica and/or alumina, and then formed into desiredshapes (e.g., extrudates, pellets, rings, etc.) by extrusion or othersuitable methods. Metal ions such as aluminum, titanium, vanadium,zirconium, gallium, copper, manganese, zinc, nickel, iron, cobalt,germanium, chromium and molybdenum may be added to the catalyst byimpregnation, ion exchange, or by replacing a part of the lattice atomsas described in G. W. Skeels and E. M. Flanigen in M. Occelli, et al.,eds., A.C.S. Symposium Series, Vol. 398, Buttersworth, pp. 420-435(1989).

The composition of the invention is characterized by means of XRD, gasadsorption, ²⁷Al-NMR and NH₃-IR (infrared). XRD and ²⁷Al-NMR show thatthe zeolite structure remains unchanged after being incorporated into,or supported on, siliceous mesoporous material. However, NH₃-IR show thechanges of hydroxyl groups after the incorporation of zeolite Beta. Theextent of such changes of hydroxyl groups also depends on the zeoliteloading in the final composite. While not wishing to be bound to anyparticular theory, it is believed that the interaction of zeolite withmesoporous matrix/support leads to a unique structure that is distinctlydifferent from a simple, linear combination of the zeolite andmesoporous material. Moreover, the FTIR data shows that there is afrequency shift of the hydroxyl groups, consistent with an aciditymodification.

In principle, the catalyst described herein can be used in all theprocesses in which zeolite-based catalyst is typically employed. Forexample, ZSM-11 can be used in virtually all of the reactions that arecatalyzed by ZSM-5 (e.g., aromatics alkylation, xylene isomerization,dewaxing, etc.); ZSM-12 can be used in the processes of aromaticsalkyation (e.g., production of p-diisopropylbenzene), aromatization,isomerization, dewaxing, etc.; ZSM-20 can be used in isomerization,alkene production, hydrocracking, and aromatization; ZSM-22 and ZSM-23are useful for isomerization, alkene production, hydrocracking, andaromatization; ZSM-34 is useful for catalyzing methanol to olefins;ZSM-35 is useful for dewaxing, isomerization, aromatization, crackingand hydrogenation; ZSM-48 is useful for isomerization; PSH-3 and MCM-22are active for aromatic alkylation, cracking, isomerization,aromatization, etc.; ITQ-1 can be used for cracking, oxidation, etc.;ITQ-2 is especially useful for cracking, hydration, alkylation, etc.;ITQ-21 is a very good catalyst for cracking; SAPO-5 is used inisomerization, dehydration, cracking; SAPO-34 is useful fordehydrogenation; SAPO-11 is useful for dewaxing and aromaticsisomerization.

For example, catalytic cracking of petroleum feedstock (e.g. gas oil andvacuum gas oil) using a catalyst described herein can be carried out inFCC or TCC units at a temperature of from about 400° C. to about 650°C., a catalyst to feed weight ratio from about 3:1 to 10:1. Feeds forcatalytic cracking can include petroleum fractions having an initialboiling point (IBP) of from about 200° C. to about 260° C. and an endboiling point (EBP) of from about 400° C. to about 455° C. Optionally,the feed can include petroleum fractions having components with boilingpoints above 540° C., such as deasphalted and undeasphalted petroleumresidue, tar sand oil, shale oil, bitumen, or coal oil.

Alkylation of organic compounds with olefins employing catalystdescribed herein can be performed at a temperature of from about 90° C.to about 250° C., a pressure of from about 0.5 bar to about 35 bars, anda space velocity of from about 1 WHSV to about 20 WHSV.

Hydrocracking of hydrocarbons employing the catalyst described hereincan be performed under reaction conditions including a temperature offrom about 200° C. to about 400° C., a pressure of from about 10 bars toabout 70 bars, and a space velocity of from about 0.4 WHSV to about 50WHSV.

Hydroisomerization of hydrocarbons employing the catalyst describedherein can be performed under reaction conditions including atemperature of from about 150° C. to about 500° C., a pressure of fromabout 1 bar to about 240 bars, and a space velocity of from about 0.1WHSV to about 20 WHSV.

Catalytic dewaxing of hydrocarbons employing the catalyst describedherein can be performed under a wide range of reaction conditions, e.g.,a temperature of from about 150° C. to about 500° C., a pressure of fromabout 6 bars to about 110 bars, and a space velocity of from about 0.1WHSV to about 20 WHSV.

Acylation of organic compounds (e.g., aromatics, alkylaromatics)employing the catalyst described herein can be conducted under reactionconditions including a temperature of from about 20° C. to about 350°C., a pressure of from about 1 bar to about 110 bars, and a spacevelocity of from about 0.1 WHSV to about 20 WHSV. Acylating agentsinclude, for example, carboxylic acid anhydrides and acyl halides.

Aromatization of light hydrocarbon to aromatics using the catalystdescribed herein is preferably carried out under reaction conditionsincluding a temperature of from about 600° C. to about 800° C., apressure less than about 14 bars, and a space velocity of from about 0.1WHSV to about 10 WHSV.

In some particular applications, the composition of the invention willshow even more advantages than the conventional catalysts. For example,catalytic cracking of heavy feeds ideally needs some mild acidity on themesoporous matrix/support, which can achieve pre-cracking of the verylarge molecules into moderate-sized molecules, and consequently themoderate-sized molecules further crack into the desired products. Thecomposition of the invention may contain metals (e.g., aluminum) in theframework of the mesoporous matrix/support, offering mild acidity.Moreover, the high pore volume and high surface area provided by themesoporous matrix/support can improve the tolerance to metals (e.g., V,Ni, Fe) and to sulfur, nitrogen, and oxygen species. Furthermore, thecomposition of the invention can be easily tuned by varying the type ofzeolites employed, the amount of zeolite loading, and the mesoporosity,to meet some particular requirements for the processes.

The composition of the invention containing some metals (e.g., Ni, W,Pt, Pd, and combinations thereof) having (de)hydrogenation functions canbe used as a catalyst for hydrocracking. The balance between thecracking activity and hydrogenation activity can be easily achieved byappropriate selection of the zeolite loading, the amount of metals inmesoporous matrix/support offering acidity, and the amount of metalswith hydrogenation function. Normally, zeolite material has highcracking activity, and mesoporous materials have lower crackingactivity. As such, the combination of zeolite and mesoporous matrix canbe adjusted to provide the desired cracking activity. Therefore, theyield and selectivity can be optimized. For example, a high selectivityfor middle distillate or diesel fuel can be achieved. In the productionof lube base oils, the composition of the invention allows a range offeedstocks to be broadened, because mesoporous matrix/support offersprecracking activity; it also improves the tolerance to heavy metals andother poisoning species.

The method of making the catalyst composition and the application of thecatalytic composition of the present invention are illustrated by thefollowing examples, but are not limited to these examples. In theseexamples the composition amounts are given in parts by weight.

EXAMPLE 1

First, 1.5 parts calcined zeolite beta with an Si/Al molar ratio of 25and an average particle size of 1 μm were suspended in 16.3 parts waterand stirred for 30 minutes. Then 20.3 parts tetraethylorthosilicate(TEOS) were added to the suspension with stirring. After continuousstirring for another 30 minutes, 9.3 parts triethanolamine were added.After stirring again for another 30 minutes, 4.0 partstetraethylammonium hydroxide aqueous solution (35% solution availablefrom Aldrich) were added drop-wise to the mixture to increase the pH.After stirring for about 2 hours, the mixture formed a thick non-flowinggel. This gel was aged at room temperature under static conditions for17 hours. Next, the gel was dried in air at 100° C. for 28 hours. Thedried gel was transferred into an autoclave and hydrothermally treatedat 170° C. for 17.5 hours. Finally, it was calcined at 600° C. for 10hours in air with a ramp rate of 1° C./min.

The final product was designated as Sample 1. The theoretical amount ofzeolite beta present in the Sample 1 was 20 wt %. Sample 1 wascharacterized by XRD, TEM nitrogen porosimetry, argon porosimetry andNH₃-temperature programmed desorption (TPD). Pure zeolite beta was alsocharacterized by XRD for purposes of comparison.

Referring to FIG. 1, the XRD pattern of the pure zeolite beta, depictedin plot 1-b, shows the most pronounced characteristic reflections atabout 7.70 and 22.2° in 2 theta (θ) with a 33 minute scanning time. TheXRD pattern of the mesoporous inorganic oxide support with the zeolitebeta crystals (Sample 1) is depicted in plot 1-a. An intense peak at lowangle is observed, indicating that Sample 1 is a meso-structuredmaterial. The peaks for zeolite beta are relatively small because themaximum theoretical zeolite content of the final product is only about20 wt %. When the scanning time for Sample 1 was extended to 45 hours,the characteristic peaks of zeolite beta become clearly visible, asdepicted in plot 1-c.

Referring now to FIG. 2, a high-resolution TEM image of Sample 1 isdepicted, which shows dark gray domains 11 in a mesoporous matrix 12.The inset “ED” depicts an electron diffraction pattern that confirmsthat the dark gray domains 11 are zeolite beta crystals.

Nitrogen adsorption shows that Sample 1 has a narrow mesopore sizedistribution, mainly centered at about 9.0 nm, high surface area of 710m²/g and high total pore volume of 1.01 cm³/g. Argon adsorption shows apeak of micropore size distribution around about 0.64 nm, correspondingto micropore size in zeolite beta. The micropore volume of pores with adiameter smaller than 0.7 nm was 0.04 cm³. This is about 16% of themicropore volume of the pure zeolite beta. Initial addition ofuncalcined zeolite beta was 20 wt % based on the final composite. Thezeolite beta weight decreased by about 20 wt % due to the templateremoval during calcination. Taking the mass loss of zeolite duringcalcination into account, the expected content of zeolite beta in thefinal composite is about 16 wt %, which is consistent with the valueobtained from micropore volume.

Referring to FIG. 3, the NH₃-TPD measurement of Sample 1 showed twodesorption peaks, indicating that there are strong acid sites similar tothose in zeolites.

EXAMPLE 2

First, 3.4 parts calcined zeolite beta with an Si/Al ratio of 150 and anaverage particle size of 0.2 μm were suspended in 85.0 parts water andstirred for 30 minutes. Then 105.8 parts TEOS were added to thesuspension with stirring. After continuous stirring for another 30minutes, 38.3 parts triethanolamine were added. After stirring again foranother 30 minutes, 20.9 parts tetraethylammonium hydroxide aqueoussolution (35%) were added drop-wise to the mixture. After stirring forabout 2 hours the mixture turned into a thick non-flowing gel. This gelwas aged at room temperature under static conditions for 24 hours. Next,the gel was dried in air at 98-100° C. for 24 hours. The dried gel wastransferred into autoclaves and hydrothermally treated at 180° C. for 4hours. Finally, it was calcined at 600° C. for 10 hours in air with aramp rate of 1° C./min. The XRD pattern of the resultant product,designated as Sample 2, is shown in FIG. 5. There was about 10 wt %zeolite beta in the final composite.

EXAMPLE 3

First, 4.6 parts calcined zeolite beta with an Si/Al ratio of 150 and anaverage particle size of 0.2 μm were suspended in 51.02 parts water andstirred for 30 minutes. Then 23.0 parts triethanolamine were added tothe suspension with stirring. After continuous stirring for another 30minutes, 63.5 parts TEOS were added. After stirring again for another 30minutes, 12.6 parts tetraethylammonium hydroxide aqueous solution (35%)were added drop-wise to the mixture. After stirring for about 2 hours,the mixture formed a thick, non-flowing gel. This gel was aged at roomtemperature under static conditions for 24 hours. Next, the gel wasdried in air at 100° C. for 24 hours. The dried gel was transferred intoautoclaves and hydrothermally treated at 180° C. for 4 hours. Finally,it was calcined at 600° C. for 10 hours in air with a ramp rate of 1°C./min. The XRD pattern of the resultant product, designated as Sample3, is shown in FIG. 5, which clearly shows two characteristic peaks ofzeolite beta. There is about 20 wt % zeolite beta in the finalcomposite. Nitrogen adsorption revealed its surface area of about 730m²/g, pore volume of about 1.08 cm³/g. The mesopore size distribution ofSample 3 is shown in FIG. 4.

EXAMPLE 4

First, 12.2 parts calcined zeolite beta with an Si/Al ratio of 150 andan average particle size of 0.2 μm were suspended in 51.0 parts waterand stirred for 30 minutes. Then 23.0 parts triethanolamine were addedto the suspension with stirring. After continuous stirring for another30 minutes, 63.5 parts TEOS were added. After stirring again for another30 minutes, 12.7 parts tetraethylammonium hydroxide aqueous solution(35%) were added drop-wise to the mixture. After stirring for about 2hours, the mixture formed a thick non-flowing gel. This gel was aged atroom temperature under static conditions for 24 hours. Next, the gel wasdried in air at 100° C. for 24 hours. The dried gel was transferred intoautoclaves and hydrothermally treated at 180° C. for 4 hours. Finally,it was calcined at 600° C. for 10 hours in air with a ramp rate of 1°C./min. The XRD pattern of the resultant product, designated at Sample4, is shown in FIG. 5, which clearly shows two characteristic peaks ofzeolite beta. There is about 40 wt % zeolite beta in the finalcomposite. Nitrogen adsorption revealed its surface area of about 637m²/g, pore volume of about 1.07 cm³/g. Its mesopore size distribution isshown in FIG. 4.

EXAMPLE 5

First, 9.2 parts calcined zeolite beta with an Si/Al ratio of 150 and anaverage particle size of 0.2 μm were suspended in 17.0 parts water andstirred for 30 minutes. Then 7.6 parts triethanolamine were added to theabove suspension under stirring. After continuous stirring for another30 minutes, 21.2 parts TEOS were added. After stirring again for another30 minutes, 4.2 parts of tetraethylammonium hydroxide aqueous solution(35%) were added drop-wise to the mixture. After stirring for about 2hours, the mixture formed a thick, non-flowing gel. This gel was aged atroom temperature under static conditions for 24 hours. Next, the gel wasdried in air at 100° C. for 24 hours. The dried gel was transferred intothree 50 ml autoclaves and hydrothermally treated at 180° C. for 4hours. Finally, it was calcined at 600° C. for 10 hours in air with aramp rate of 1° C./min. The XRD pattern of the resultant product,designated as Sample 5, is shown in FIG. 5, which clearly shows twocharacteristic peaks of zeolite beta. There was about 60 wt % zeoliteBeta in the final composite. Nitrogen adsorption revealed its surfacearea of about 639 m²/g, pore volume of about 0.97 cm³/g. Its mesoporesize distribution is shown in FIG. 4.

EXAMPLE 6

Eight parts of Sample 1 were mixed with two parts of alumina in the formof Nyacol to provide a catalyst. The mixture was dried and calcined byraising the temperature to 120° C. at the rate of 5° C./min, maintainingthe 120° C. temperature for one hour, then raising the temperature atthe rate of 5° C./min to 500° C. for five hours and finally lowering thetemperature at the rate of 5° C./min to 150° C. and then allowing thecatalyst to cool to room temperature in a desiccator. The catalyst wasthen manually crushed and sieved to −12/+20 mesh for activity testing.This catalyst contained 16 wt % zeolite beta in mesoporous support. Arecirculating differential fixed-bed reactor was charged with 1.0 gramof catalyst. The recirculating rate (200 g/min) was about 33 times thefeed rate (6.1 g/min). The loaded reactor was initially filled withbenzene, the feed (benzene containing 0.35 wt % ethylene) was metered inwith a metering pump when the reactor reached 190° C. The run wascarried out for seven hours. The reaction conditions included atemperature of 190° C. a pressure of 350 psig and a space velocity of 6WHSV. Feed samples were taken at the beginning, the middle and the endof the run. Product samples were taken every third minute and analyzedby gas chromatography. Based on a first-order rate equation, a rateconstant of 0.30 cm³/g-sec was obtained for the benzene alkylation withethylene to form ethylbenzene for 16 wt % zeolite beta-containingcatalyst. Alternatively, this value is equivalent of a value of 1.50cm³/g-sec for an 80 wt % of zeolite beta-catalyst.

COMPARISON EXAMPLE A

A wholly siliceous mesoporous support was made in accordance with themethod described in Example 1 except that no zeolite was incorporated.The resulting support was designated as Comparison Sample A. An NH₃-TPDmeasurement was made of Comparison Sample A, and the resultingmeasurement is depicted in FIG. 3.

COMPARISON EXAMPLE B

A sample of zeolite beta obtained from a commercial supplier andcontaining 80 wt % zeolite beta (Si/Al ratio of 4.9) and 20% binder wasresized to −12/+20 mesh. The pore size distribution of zeolite beta isdepicted in FIG. 4. The activity of the pure zeolite beta of thisComparison Example was tested in the same alkylation reaction using thesame methodology and apparatus described in Example 6 above. Afirst-order rate constant of 0.29 cm³/g-sec was obtained.

Comparing the results of Example 6 with Comparison Example B, thecatalyst of Example 6, which is in accordance with the presentinvention, has about five times greater activity than an equivalentamount of zeolite beta alone for the alkylation of benzene withethylene. These results indicate that the integrity of the zeolitecrystals in the mesoporous catalyst support is maintained during thesynthesis of Sample 1. The results also demonstrate that the microporouszeolite beta in the mesoporous support of Sample 1 was still accessibleafter the synthesis of the catalyst and that the mesopores of thesupport facilitate mass transfer in aromatic alkylation reactions.

EXAMPLE 7

This example illustrates incorporation of MCM-22. First, 2.4 partsas-synthesized zeolite MCM-22 with an Si/Al ratio of 12.8 and an averageparticle size of 2.5 μm were suspended in 10.5 parts water and stirredfor 30 minutes. Then 9.2 parts triethanolamine were added to the abovesuspension under stirring. After continuous stirring for another 30minutes, 12.7 parts TEOS were added. After stirring again for another 30minutes, 2.52 parts tetraethylammonium hydroxide aqueous solution (35%)were added drop-wise to the mixture. After stirring for about 2 hours,the mixture formed a thick, non-flowing gel. This gel was aged at roomtemperature under static conditions for 24 hours. Next, the gel wasdried in air at 98° C. for 24 hrs. The dried gel was transferred intoautoclaves and hydrothermally treated at 180° C. for 4 hours. Finally,it was calcined at 600° C. for 10 hours in air with a heating ramp rateof 1° C./min.

The XRD pattern of the resultant product, designated as Composite 7 andshown as plot 6-c in FIG. 6, clearly shows characteristic peaks ofzeolite MCM-22 (plot 6-b) and mesoporous material (plot 6-a). There isabout 40 wt % zeolite MCM-22 in Composite 7, and elemental analysisconfirmed this number based on aluminum content, assuming no aluminumfrom siliceous mesoporous material. Nitrogen adsorption revealed itssurface area of about 686 m²/g, pore volume of about 0.82 cm³/g. Itsmesopore size distribution centered around 10 nm in FIG. 7. Argonadsorption showed micropores centered around 0.5 nm.

EXAMPLE 8

This example illustrates incorporation of MCM-56. First, 7.7 partstriethanolamine were mixed with 8.5 parts of distilled water for half anhour. Then, 2.0 parts of the NH₄ ⁺-form zeolite MCM-56 (Si/Al molarratio of 12.5) were added into the above solution under stirring. Aftercontinuous stirring for another 2 hours, 10.6 parts TEOS were addedwhile stirring. After stirring again for another 30 minutes, 2.1 partsof tetraethylammonium hydroxide aqueous solution (35%) were addeddrop-wise to the mixture. The stirring continued until the mixtureformed a thick, non-flowing gel. This gel was treated as same as that inExample 7 to get white powder.

The XRD pattern of the resultant product, designated as Composite 8,shown as plot 8-c in FIG. 8, which clearly shows two characteristicpeaks of zeolite MCM-56 and mesoporous material. Plot 8-b depicts theXRD pattern of zeolite MCM-56, and plot 8-a depicts the XRD pattern ofmesoporous material. Elemental analysis showed that the total Si/Alratio of the final composite was 43 and that the zeolite loading wasabout 33.3 wt % in the final composite. Nitrogen adsorption revealed itssurface area of about 712 m²/g and a pore volume of about 0.96 cm³/g.Its mesopore size distribution centered around 2.0 nm, shown in FIG. 7.

EXAMPLE 9

This example illustrates incorporation of ITQ-2. First, 15.2 parts ofcetyltriethylammonium bromide (CTAB) was dissolved into 31.7 parts ofwater together with 32.7 parts of tetrapropylammonium hydroxide. Then2.7 parts of as-synthesized MCM-22 was added into the above solution toget a suspension. The suspension was stirred in a flask placed in an 80°C. oil bath with reflux condenser for 18 hours to swell the lamellarstructured zeolite MCM-22. The swollen MCM-22 was delaminated in anultrasonic bath (135 w, 40 KHz) for an hour to get ITQ-2 zeolite. TheITQ-2 zeolite was washed and centrifuged until the pH value of thesuspension dropped down to 8.

ITQ-2 was re-suspended in 10 parts of water and then added into amixture consisting of 9.2 parts of TEA and 12.7 parts of TEOS understirring. After about 45 minutes a thick gel formed. The gel was treatedthe same as that in Example 7. The XRD pattern of the final composite,designated as Composite 9 and shown as plot 9-c in FIG. 9, clearly showstwo characteristic peaks of zeolite ITQ-2 and mesoporous material. Plot9-b depicts the XRD pattern of mesoporous material, and plot 9-a depictsthe XRD pattern of zeolite ITQ-2. Elemental analysis showed that thetotal Si/Al ratio of the final composite was 36.9 and that the zeoliteloading was about 32.3 wt % in the final composite. Nitrogen adsorptionrevealed a surface area of about 685 m²/g, and a pore volume of about0.40 cm³/g. Its mesopore size distribution centered on 2.1 nm.

EXAMPLE 10

This example illustrates an “in-situ” incorporation of ITQ-2, in whichMCM-22 transformation to ITO-2 was conducted in the course of mesoporeformation. The chemicals and their amount of chemicals used were thesame as in Example 9. First, as-synthesized MCM-22 was swollen in thesame way as in Example 9. However, the swollen MCM-22 was notimmediately delaminated. It was washed and subsequently centrifugeduntil no bromide was detected using silver nitrate solution. The swollenMCM-22 was re-suspended in water.

A bottle with a mixture consisting of TEA and TEOS was placed in anultrasonic bath. The mixture was stirred by both sonication and amechanical Teflon stirrer, meanwhile the swollen MCM-22 suspension wasadded. After about an hour of stirring, 2.5 parts of TEAOH (35%,tetraethyl ammonium hydroxide) was added and finally a thick gel formed.The gel was treated the same as that in Example 7. The XRD pattern ofthe final composite, designated as Composite 10 and shown as plot 9-d inFIG. 9, clearly shows two characteristic peaks of zeolite ITQ-2 (plot9-a) and mesoporous material (plot 9-b). Elemental analysis showed thatthe total Si/Al ratio of Composite 10 was 32.4 and that the zeoliteloading was about 50 wt % in the final composite. Nitrogen adsorptionrevealed its surface area of about 726 m²/g, pore volume of about 0.78cm³/g. The mesopore size distribution was centered on 2.2 nm, as shownin FIG. 7.

EXAMPLE 11

Acylation of 2-methoxynaphthalene to 2-acetyl-6-methoxynaphthalene wasperformed in a stirred batch reactor. The reactor with 16.5 parts ofcatalyst, i.e., Composite 10 made in Example 10, was heated at 240° C.under vacuum for 2 hours and then filled with dry nitrogen. After thereactor was cooled down to 120° C., 250 parts of decalin (as a solvent),31.6 parts 2-methoxynaphthalene, 40 parts of acetic anhydride and 10parts of n-tetradecane (as an internal standard) was injected into thereactor. After reaction for six hours, the reactor mixture was analyzedby GC with WAX 52 CB column, and it was found that the conversion of2-methoxynaphthalene reaches 56% with 100% selectivity to2-acetyl-6-methoxynaphthalene.

EXAMPLE 12

Various catalysts made in the above examples were used to performacylation of 2-methoxynaphthalene to 2-acetyl-6-methoxynaphthalene. Thereaction conditions were the same as that in Example 11. In all teststhe amount of zeolites in the reactor were kept the same as that inExample 11. In other words, the amount of catalyst (composite) wasdifferent due to different zeolite loading in the composites. Table 1shows the comparison of reaction results over different catalysts.

TABLE 1 Comparison of acylation of 2-methoxynaphthalene on differentcatalysts Zeolite Si/Al Con- Catalyst Loading Ratio version SelectivityCatalyst Description % in Zeolite (%) (%) Composite 7 MCM-22 40.0 12.828.5 96 Composite Composite 8 MCM-56 33.3 12.5 53.4 96 CompositeComposite 10 ITQ-2 50.0 12.8 56.2 96 Composite

EXAMPLE 13

Cracking of n-hexane was carried out in a fixed bed reactor. About 1 gof Sample 3, with a particle size of 125-250 μm obtained by crushing andsieving, was introduced into the reactor. For activation, the sample washeated in an air flow of 50 ml/min from room temperature to 600° C. witha heating rate of 10° C./min and held there for 8 hours. The crackingreaction of n-hexane was carried out under atmospheric pressure and witha n-hexane concentration of 6.6 mol % in nitrogen. The reactiontemperature was varied from 500° C. to 570° C. in steps of 10° C. Themodified contact time based on the mass of catalyst was kept constant at1.4 g_(cat)*min*l⁻¹. For all measurements the n-hexane conversion wasbelow 15% to avoid deactivation. It was found that the cracking ofn-hexane could be described with apparent first order kinetics, and thefirst order reaction rate constants based on the zeolite mass werecalculated for the different reaction temperatures. To compare thecatalyst activities the reaction rate constant for 538° C. has beencalculated with the Arrhenius equation that has been determined fromfour first order reaction rate constants. For Sample 3 the obtainedreaction rate was 0.19 g_(zeolite) ⁻¹*min⁻¹*l.

A comparison was made with pure beta zeolite, and Samples 4 and 5 asfollows:

A commercial zeolite beta with a Si/Al ratio of 150 was pressed intotablets and sieved to 125-250 μm. The activity of this pure zeolitebeta, and those of Samples 4 and 5, were tested using the samemethodology and apparatus described in Example 7 above. The reactionrate constants based on the mass of zeolite that characterize theactivities of the catalysts are shown in FIG. 10. The activities ofSample 3, 4, and 5 are about two times higher than the activity of purezeolite beta. The relative high activation energies of 150 kJ/mol, whichhave been measured, indicate that mass transfer did not influence thereaction of the relatively small n-hexane molecules.

EXAMPLE 14

FTIR spectra of the mesoporous support and pure zeolite Beta (Samples 3,4, and 5) were recorded with a Bruker IFS88 spectrometer at a resolutionof 4 cm⁻¹. All the samples were pelletized with KBr and placed in quartzcells permanently connected to a vacuum line (ultimate pressure≦10⁻⁵Torr) for thermal treatments under in situ conditions.

Referring to FIG. 11, the intensive peak at 3745 cm⁻¹ is conventionallyassigned to silanol groups; a very small peak at 3610 cm⁻¹ (especiallyfor zeolite Beta) can be assigned to its Bronsted acid sites, and thebroad absorptions in the 3725-3650 cm⁻¹ region can be assigned to eitherH-bonded silanols or silanols close to Lewis acid centers. In general,the composition of the invention (Samples 3, 4, 5) showed a broadabsorption in the 3725-3650 cm⁻¹ range compared to the zeolite Beta usedand mesoporous support considered individually. It is interesting tonote that the composite with 40 wt % zeolite Beta has the broadestdistribution of hydroxyls in the 3725-3650 cm⁻¹ range. Moreover, theintensity of these hydroxyls is higher than in the other samples. FIG.11 clearly shows that the composite with 40 wt % zeolite is distinctlydifferent from either the mesoporous support or the pure zeolite Beta.

While not wishing to be bound to any particular theory, it is believedthat the interaction between the nano-sized zeolite and the mesoporousmatrix forms a unique, third structure that is different from a simple,linear combination of zeolite and mesoporous material. Moreover, thereis a frequency shift of the hydroxyl group, consistent with an aciditymodification. This can explain why 40 wt % zeolite loading has apronounced change in acidity. This may be associated catalytic activitywith respect to cracking of n-hexane in Example 13.

EXAMPLE 15

An ultrastable Y (USY) having a Si/Al molar ratio of 14.8 and a surfacearea of 606 m²/g was incorporated into an aluminum-containing mesoporousmatrix. First, 9.2 parts ultrastable zeolite Y were suspended in 17.0parts water and stirred for 30 minutes. Then 7.7 parts triethanolaminewere added to the above suspension under stirring. After continuousstirring for another 30 minutes, another mixture containing 21.2 partsof TEOS and 3.3 parts of aluminum isopropoxide were added understirring. After stirring again for another 30 minutes, 4.2 partstetraethylammonium hydroxide aqueous solution (35%) were added drop-wiseto the mixture. After stirring for about 2 hours, the mixture formed athick non-flowing gel. This gel was aged at room temperature understatic conditions for 24 hours. Next, the gel was dried in air at 100°C. for 24 hours. The dried gel was transferred into an autoclave andhydrothermally treated at 180° C. for 2 hours. Finally, it was calcinedat 600° C. for 10 hours in air with a ramp rate of 1° C./min. The finalmaterial was designated as composite 15.

The XRD pattern of composite 15 is shown as plot 12-a in FIG. 12, whichclearly shows two characteristic peaks of zeolite Y and mesostructurematerial. Plot 12-b depicts an XRD pattern of zeolite Y. There is about60 wt % zeolite Y in the final composite. Nitrogen adsorption revealedits surface area of about 689 m²/g, pore volume of about 0.99 cm³/g.

EXAMPLE 16

A catalytic cracking catalyst is prepared using Composite 15. The protonform (H⁺−) of the composite is obtained by ion-exchange, mixing one partof Composite 15 with ten parts of 1 N ammonium nitrate solution at 60°C. for 6 hours while stirring. The solid material is filtered, washedand dried at 110° C. to get a white powder. After a second ion-exchange,the solid material is calcined at 550° C. for 6 hours in air.

Eight parts of H⁺−Composite 15 are mixed with two parts of alumina inthe form of Nyacol to provide a catalyst. The mixture is dried andcalcined by the following steps: (a) raising the temperature to 120° C.at the rate of 5° C./min, (b) maintaining the 120° C. temperature forone hour, (c) raising the temperature at the rate of 5° C./min to 500°C. for five hours, (d) lowering the temperature at the rate of 5° C./minto 150° C., and (e) then allowing the catalyst to cool to roomtemperature in a desiccator. The catalyst contains about 48% USYzeolite.

The catalyst was then steamed for 10 hours at 760° C. with 50% steam atatmospheric pressure. The final catalyst (containing USY, mesoporousmatrix, and alumina binder) is designated as CAT16A.

For cracking activity comparison, a catalyst designated as CAT16Bcontaining 48% of USY and binder alumina (without the mesoporous matrix)is prepared by ion-exchange, extrusion and steaming in the same way asin preparation of CAT16A.

Half each of these two catalysts are impregnated with vanadiumnaphthenate in toluene, resulting in 5000 ppm vanadium deactivation ofFCC catalyst under commercial conditions. These two impregnatedcatalysts are designated as CAT16AV and CAT16BV, respectively.

EXAMPLE 17

The four catalysts prepared in Example 16 are evaluated for crackingactivity using the fluidized activity test (“FAI”) with fixed-fluidizedbed FCC units at 400° C., catalyst/oil ratio of 2, 5 minutes on stream.The feed is Light East Texas Gas Oil (LETGO), and its properties areshown in Table 2. Comparison of Catalytic performance is shown in Table3.

TABLE 2 Light East Texas Gas Oil (LETGO) properties API 36.4Distillation (D1160): IBP, (vol %) 235° C. 10% 254° C. 30% 268° C. 50%287° C. 70% 307° C. 90% 341° C. EBP 364° C. Bromine No. 0.50 KV @ 100°C., cSt 1.30 Avg. Molecular weight 269 Pour Point, ° C. −7 CCR, wt %0.02 Refractive Index @ 70° 1.4492 Aniline Point, ° C. 76 Hydrogen, wt %13.3 Sulfur, wt % 0.13 Total Nitrogen, ppm 300 Basic Nitrogen, ppm 45Nickel, ppm 0.1 Vanadium, ppm 0.1 Iron, ppm 0.77 Copper, ppm 0.05Paraffins, wt % 44.7 Naphthenes 33.2 Aromatics, wt % 22.1

TABLE 3 Catalytic Performance Vanadium FAI % Activity Catalyst Content %Conversion Retention % CAT16A 0 65.6 CAT16AV 0.52 51.3 78.7 CAT16B 048.3 CAT16BV 0.53 23.8 49.3

The results in Table 3 show that compositions of the invention improvedthe tolerance of heavy metals due to the acidic mesoporous matrix.Cracking activity is also improved by the novel combination of zeoliteand acidic mesoporous matrix.

EXAMPLE 18

A composite, designated as Composite 18, containing USY zeolite wassynthesized in the same way as described in Example 15. The onlydifference was the amount of chemicals used: 2.9 parts of USY zeolite,28 parts of aluminum isopropoxide, 171.4 parts of tetraethylorthosilicate, 34 parts of tetraethylammonium hydroxide, 124 parts oftriethanolamine and 138 parts of water. The XRD pattern of Composite 18is shown in FIG. 12, which clearly shows two characteristic peaks ofzeolite Y and mesostructured material. The composite contained about 5wt % USY zeolite, had a surface area of about 694 m²/g, and a porevolume of about 1.1 cm³/g.

The composite 18 was ion-exchanged into the proton form (H⁺−) andextruded in the same way as described in Example 16. Finally, Composite18 was formed into a cylindrical shape with a 1.6 mm diameter andcontained about 4 wt % USY, 76 wt % of Al-containing mesoporous materialand 20 wt % Al₂O₃.

Composite 18 was further functionalized by impregnation with Ni and W.Five (5) parts of nickel nitrate aqueous solution (14 wt % Ni) was mixedwith 8.4 parts of ammonium metatungstate solution (39.8 wt % W) understirring. The mixture was then diluted with 9 parts of water understirring. 12.5 Parts of Composite 18 were impregnated with the aboveNi/W solution, dried at 118° C. for 2 hours and calcined at 500° C. for2 hours. The resulting modified Composite 18 was designated as CAT 18and contained 4.0 wt % of Ni and 18.7 wt % W. It mainly featured a highamount of weakly acidic mesoporous matrix.

EXAMPLE 19

This Example illustrates the use of the material of Example 18 as ahydrocracking catalyst. Composite 18 prepared in Example 18 is evaluatedfor middle distillates selectivity in hydrocracking. The evaluation iscarried out in a flow reactor with presulfided Composite 18 (in aconventional way) using a hydrotreated heavy vacuum gas oil as afeedstock. It is operated at LHSV of 1.5 kg/liter hour, total pressureof 140 bar (partial pressure of H₂S of 5.5 bar, and a partial pressureof ammonia of 0.075 bar) and a gas/feed ratio of 1500 NL/kg. Theproperties of feedstock are shown in Table 4.

TABLE 4 Hydrotreated Heavy Vacuum Gas Oil Properties Distillation(D1160): IBP, ° C.(vol %) 345 10% 402 30% 441 50% 472 70% 508 90% 564 EP741 KV @ 100° C., cst 8.81 Carbon, wt % 86.7 Hydrogen, wt % 13.4 Totalsulfur, wt % 0.008 Total Nitrogen, ppm 16.1

The selectivity for middle distillates (e.g. boiling point range from175° C. to 345° C.) is assessed at a net conversion of components of 65wt %. Surprisingly, the selectivity reaches 72.6 wt %.

While the above description contains many specifics, these specificsshould not be construed as limitations on the scope of the invention,but merely as exemplifications of preferred embodiments thereof. Thoseskilled in the art will envision many other possibilities within thescope and spirit of the invention as defined by the examples.

1. A composition comprising: a) at least one type of ordered, crystalline and microporous material with an average pore diameter less than 20 Angstroms; b) at least one type of non-crystalline inorganic oxide, said inorganic oxide having mesopores or mesopores and micropores and, wherein said inorganic oxide has a peak in an X-ray diffraction pattern between 0.5 and 2.5 degrees in 2θ, and wherein said mesopores are interconnected mesopores.
 2. The composition of claim 1 wherein the said crystalline microporous materials are selected from a group consisting of zeolite Beta, zeolite Y, USY, mordenite, Zeolite L, ZSM-5, ZSM-11, ZSM-12, ZSM-20, Theta-1, ZSM-23, ZSM-34, ZSM-35, ZSM-48, SSZ-32, PSH-3, MCM-22, MCM-49, MCM-56, ITQ-1, ITQ-2, ITQ-4, ITQ-21, SAPO-5, SAPO-11, SAPO-37, Breck-6 and ALPO₄-5.
 3. The composition of claim 1 wherein the at least one inorganic oxide has at least 97 volume percent mesopores based on micropores and mesopores of the inorganic oxide, a surface area of 400-1100 m²/g, and a total pore volume of about 0.3-2.2 cm³/g.
 4. The composition of claim 3 wherein the mesopores have a size ranging from about 2 nm to about 25 nm.
 5. The composition of claim 3 wherein the porous inorganic oxide is silicon oxide.
 6. The composition of claim 1 further comprising at least one type of metal.
 7. The composition of claim 6 wherein the metal is incorporated into the zeolite framework as substitutions of lattice atoms and/or located inside the zeolite micropores.
 8. The composition of claim 6 wherein the metal is incorporated into the inorganic oxide inside at least one mesopore wall and/or on at least one mesopore surface.
 9. The composition of claim 6 wherein the metal is at least one metal selected from the group consisting of aluminum, titanium, vanadium, zirconium, gallium, boron, manganese, zinc, copper, gold, lanthanum, chromium, molybdenum, nickel, cobalt, iron, tungsten, palladium and platinum.
 10. The composition of claim 1 wherein the composition percentage by weight of the crystalline microporous material ranges from about 3% to about 90%.
 11. The composition of claim 1 wherein the composition percentage by weight of the microporous zeolite ranges from about 4% to about 80%.
 12. A method for making a catalytic material which comprises the steps of: a) pretreating a zeolite by one or more ion exchange, impregnation, immobilization of functional species and steaming; b) combining the pretreated zeolite with water, an inorganic oxide or a precursor of an inorganic oxide, and at least one mesopore-forming organic compound to form a mixture; c) drying the mixture; d) heating the dried mixture to a temperature and for a period of time sufficient to form a mesoporous inorganic oxide structure.
 13. The method of claim 12 wherein the mesopore-forming organic compound is selected from the group consisting of glycerol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, triethanolamine, triisopropanolamine, starch, sulfolane, tetraethylene pentamine and diethylene glycol dibenzoate.
 14. The method of claim 12 wherein said mesopore-forming organic compound has a boiling point of at least 150° C.
 15. The method of claim 12 wherein the inorganic oxide is formed by reacting an inorganic oxide precursor with water.
 16. The method of claim 12 wherein the mixture is maintained at a pH above about 7.0.
 17. The method of claim 14 wherein the mixture is dried by heating in air at a temperature and for a period of time sufficient to drive off at least a major portion of the water and mesopore-forming organic compounds.
 18. The method of claim 12 wherein the heating step (d) comprises heating the dried mixture to a temperature of from about 100° C. to about 250° C.
 19. The method of claim 12 further comprising the step of calcining the heated dried mixture at a temperature of from about 300° C. to about 1000° C. for at least a period of time sufficient to effect removal of the mesopore-forming organic compound from the mesoporous, inorganic oxide support.
 20. The method of claim 12 further comprising combining metal ions with the mixture, the metal being selected from the group consisting of aluminum, titanium, vanadium, zirconium, gallium, boron, manganese, zinc, copper, gold, lanthanum, chromium, molybdenum, nickel, cobalt, iron, tungsten, palladium and platinum.
 21. The method of claim 12 further comprising the steps of admixing a binder with the catalytic material and forming the catalytic material into a predetermined shape.
 22. The composition of claim 1 wherein the said crystalline microporous materials are selected from a group consisting of zeolite Y, USY, mordenite, Zeolite L, ZSM-5, ZSM-11, ZSM-12, ZSM-20, Theta-1, ZSM-23, ZSM-34, ZSM-35, ZSM-48, SSZ-32, PSH-3, MCM-22, MCM-49, MCM-56, ITQ-1, ITQ-2, ITQ-4, ITQ-21, SAPO-5, SAPO-11, SAPO-37, Breck-6 and ALPO₄-5.
 23. The method of claim 12 wherein the mesoporous inorganic oxide structure has interconnected mesospores characterized by a peak in an X-ray diffraction pattern between 0.5 and 2.5 degrees in 2θ. 